STRUCTURE
R-NH2
1° AMine
R2. NH
2° Amine
Lower aliphatic amines are gases,
intermediate members are liquid
(fishy odour), while higher members
are sold.
:
-
NH2
N2+X
NaNO + 2HCl
2

→
273 − 278K
+ NaCl + 2H2O
-
N2+X
DIAZONIUM SALTS
SOLUBILITY
Lower aliphatic amines are soluble
in wate due to H-bonding, while higher
amines (> C6) are insoluble in water.
3° Amine
:
So lub ility ∝
-
RN2+X
1
Molecular weight
CHEMICAL PROPERTIES
BOILING POINT
X
X
Ga
Primary and secondary amines
forms intermolecular H-Bonding
while tertiary does not.
N
R
PREPERATION
Colourless, soluble in water, decompose in
dry state
C6H5N2+Cl- is readily soluble in water
PHYSICAL STATE
:
Ammonia
R3N
AMINES
PHYSICAL PROPERTIES
NH3
PHYSICAL PROPERTIES
tt
an
+
Re
HX
Cu
ac
tio
n
F
R
θ > 109°
Cu
er
m
-
N X
2+
2
∆
,
Pyramidal geometry
N=N
CN
N
N/KC
CuC
O
+ H2
OH
H5 +
C 3 Cu
er
Sa
4
OH
ac
Re
ey
Ki
H 3PO 2 +
Cu
R
ti
HX
m
nd
HBF
Primary > Secondary > Tertiary
+
on
I
H2O
C
6H
5N
∆
H
2, H
+
OH
N=N
NH2
OH
PREPARATION
• Reduction of Nitro Compounds.
Sn/HCl or Fe/HCl
RNO 2 
→ RNH 2
Or H /Pol
NH
R-NC
BASIC NATURE
+
NaOH
3 → R − N H X − 
R − X 
→ R − NH 2 + H 2 O + Na+ X −
3
IN AQUEOUS PHASE
H /Ni
2
R − C ≡ N →
R − CH 2 − NH 2
Na(Hg)/C H oh
2 5
OVERALL BASICITY ORDER
O
CH
3
Cl
rb
+
yla KO
te min H
st
e
+
R'
3 Br2
H2O
O2
HN
R-NH2
Br
NH2
O
R'-
Ac
(i) CH3COCl
(ii) Br2, CH3COOH
C-
Cl
yla
(Major)
O
tio
R-NH-R'
Aliphatic Amine > Amines
> Aromatic Amines
• Reduction of Amides
R-OH
Ca
Due to the presence of lone
pair on nitrogen amines are
basic.
Factors affecting basicity
(i) Inductive effect
(ii) solvation effect
(iii) Steric hinderance
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
(C2H5)2 > (C2H5)3N > (C2H5)NH2 > NH3
• Reduction of Nitriles
ELECTROPHIC SUBSTITUTION
NH2
3° Amine > 2° Amine > 1° Amine > NH3
2
• Ammonolysis
CHEMICAL REACTION
IN GASESOUS PHASE
n
Br
NH2
R-NH-C-R'
HNO3
(i) LiAlH
4 → R − CH − NH
R − C − NH 2 
2
2
(ii) H O
2
NH2
TEST FOR AMINES
• Hoffmann Bromamide Degradation reaction
H2SO4, 288 K
NH2
NH2
+
(51%)
(47%)
NO2
NO2
O
NH2
R − C − NH 2 + Br2 + 4NaOH 
→ R − NH 2 + Na 2 CO 3 + 2NaBr + 2H 2 O
HINSBERG'S TEST
(i) CH3COCl
(ii) Br2, CH3COOH
one carbon less amine is formed as compared to amides
NO2
• Gabriel Phthalimide synthesis
O
O
C
SECONDARY AMINE
KOH

→
RX
O
SO2Cl
NaOH
→ RNH2
N - R 
C
SO2Cl
SO2-NR2
H2SO4
SO2Cl
(1° Amine)
+ RNH2
O
Aromatic primary amines cannot be prepared by this method.
anand_mani16
SO2-NHR
NH2
TERTIARY AMINE
C
N-H
C
PRIMARY AMINE
DR. Anand Mani
+ R2NH
ppt. soluble in
alkali
+ R 3N
CH3/AlCl3
or CH3OCl/AlCl3
ppt. insoluble in
alkali
https://www.anandmani.com/
SO3H
No Reaction
https://discord.io/anandmani
NO2
+
No reaction
(due to salt formation)
t.me/neetplus
(2%)